Research progress of solid porous materials for direct CO2 capture from air

doi:10.16085/j.issn.1000-6613.2022-1000

Abstract

Abstract:

Direct air capture (DAC) technology is a negative carbon technology, which is an effective supplement to the carbon capture, utilization and storage (CCUS) technology and one of the important technologies to help achieve the carbon peaking and carbon neutrality goals. Solid porous materials have irreplaceable advantages in reducing the economic cost and operating energy consumption of DAC due to their strong adsorption capacity, low regeneration energy consumption, flexible application scenarios and adjustable structure. Starting from the principles of DAC of solid porous materials, this paper focused on reviewing DAC adsorbents, such as zeolite adsorbents, silica-based adsorbents, carbon-based adsorbents, nano-alumina adsorbents, MOF adsorbents and porous resin adsorbents. The advantages and disadvantages on adsorption capacity, adsorption selectivity, hydrothermal stability, regeneration energy consumption and cycle stability of solid porous materials are introduced and compared. The effects of amine functionalization modification and carrier pore structure on the adsorption performance of CO₂ are emphatically analyzed, and specific optimization directions for the challenges faced by various solid porous materials in the application of DAC are prospected. It is pointed out that the design and development of solid porous adsorbents in the future should take both economy and efficiency into account, and further pilot-scale DAC experiments should be carried out.

Key words: direct air capture, CO₂ capture, physisorption, chemisorption, solid porous materials

摘要：

直接空气捕碳（DAC）技术属于一种负碳技术，作为碳捕集、存储和利用（CCUS）技术的有效补充，是助力实现“双碳”目标的重要技术之一。由于吸附能力强、再生能耗低、应用场景灵活以及结构可调性强，固体多孔材料在降低DAC经济成本和运行能耗方面具有不可替代的优势。本文从固体多孔材料的DAC原理出发，重点综述了包括沸石吸附剂、硅基吸附剂、炭基吸附剂、纳米氧化铝吸附剂、金属有机框架（MOF）材料吸附剂和多孔树脂材料吸附剂等DAC的研究现状，系统介绍和比较了固体多孔吸附材料的吸附容量、吸附选择性、水热稳定性、再生能耗以及循环稳定性方面的优缺点。本文着重分析了胺功能化改性和载体孔隙结构等因素对吸附CO₂性能的影响规律，对各类固体多孔材料在DAC应用中面临的挑战提出了具体的优化方向，并指出未来固体多孔吸附材料的设计开发应兼顾经济性和高效性，加快开展中试规模的DAC试验研究。

关键词: 直接空气捕集, CO₂捕集, 物理吸附, 化学吸附, 固体多孔材料

CLC Number:

TQ028

KONG Xiangru, ZHANG Xiaoyang, SUN Pengxiang, CUI Lin, DONG Yong. Research progress of solid porous materials for direct CO₂ capture from air[J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1471-1483.

孔祥如, 张肖阳, 孙鹏翔, 崔琳, 董勇. 直接空气捕碳固体多孔材料的研究进展[J]. 化工进展, 2023, 42(3): 1471-1483.

Figures/Tables 13

References 80

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载体	胺种类	CO₂浓度/气氛	吸附温度/℃	CO₂吸附量/mmol·g^-1	再生温度/℃	循环次数/性能	测量方式	参考文献
Li-LSX	—	0.0395%	25	1.34	240	—	PB	[18]
Zeolite Y8	TEPA	0.15%	30～70	3.14	—	—	PB	[19]
Zeolite Y	TEPA	0.5%	25	1.12	100	5/稳定	TGA	[20]
Zeolite 13X	—	0.04%	25	0.03（RH=49%）	140	—	TPD	[21]

载体	胺种类	CO₂浓度/气氛	吸附温度/℃	CO₂吸附量/mmol·g^-1	再生温度/℃	循环次数/性能	测量方式	参考文献
Li-LSX	—	0.0395%	25	1.34	240	—	PB	[18]
Zeolite Y8	TEPA	0.15%	30～70	3.14	—	—	PB	[19]
Zeolite Y	TEPA	0.5%	25	1.12	100	5/稳定	TGA	[20]
Zeolite 13X	—	0.04%	25	0.03（RH=49%）	140	—	TPD	[21]

载体	胺种类	CO₂浓度/气氛	吸附温度/℃	CO₂吸附量/mmol·g^-1	再生温度/℃	循环次数/性能	测量方式	参考文献
MCM-41	TRI	0.04%	25	0.98	—	—	TGA	[32]
MCM-41	TRI	0.04%	25	0.9 1.40（RH=64%）	—	—	PB	[32]
MCM-41	TRI	空气	(+5)~(-5)	1.16（RH=60%~80%）	100	3/迅速下降	TGA	[33]
SBA-15	PEI	0.04%	25	1.90	90	10/稳定	TGA	[29]
SBA-15	TEPA	0.04%	25	3.44	90	10/稳定	TGA	[29]
SBA-15+PEG200	PEI	0.04%/He	30	0.79	—	—	TGA	[31]
SBA15+PEG1000	PEI	0.04%/He	30	0.71	—	—	TGA	[31]
SBA-15+CTAB	PEI	0.04%/He	30	0.55	—	—	TGA	[31]
SBA-15	APTMS	0.04%/Ar	25	0.60	110	3/稳定	TGA	[35]
SBA-15	Aziridine	0.04%	25	1.72	110	4/稳定	MS	[36]
SBA-15	TEPA	0.04%	25	3.59（RH=49%）	—	—	TPD	[37]
Zr7-SBA-15	PEI(800)	0.04%/Ar	25	0.85	110	4/稳定	TGA	[38]
SBA-15	PEI	0.04%/Ar	25	1.05	110	3/稳定	TGA	[39]

载体	胺种类	CO₂浓度/气氛	吸附温度/℃	CO₂吸附量/mmol·g^-1	再生温度/℃	循环次数/性能	测量方式	参考文献
MCM-41	TRI	0.04%	25	0.98	—	—	TGA	[32]
MCM-41	TRI	0.04%	25	0.9 1.40（RH=64%）	—	—	PB	[32]
MCM-41	TRI	空气	(+5)~(-5)	1.16（RH=60%~80%）	100	3/迅速下降	TGA	[33]
SBA-15	PEI	0.04%	25	1.90	90	10/稳定	TGA	[29]
SBA-15	TEPA	0.04%	25	3.44	90	10/稳定	TGA	[29]
SBA-15+PEG200	PEI	0.04%/He	30	0.79	—	—	TGA	[31]
SBA15+PEG1000	PEI	0.04%/He	30	0.71	—	—	TGA	[31]
SBA-15+CTAB	PEI	0.04%/He	30	0.55	—	—	TGA	[31]
SBA-15	APTMS	0.04%/Ar	25	0.60	110	3/稳定	TGA	[35]
SBA-15	Aziridine	0.04%	25	1.72	110	4/稳定	MS	[36]
SBA-15	TEPA	0.04%	25	3.59（RH=49%）	—	—	TPD	[37]
Zr7-SBA-15	PEI(800)	0.04%/Ar	25	0.85	110	4/稳定	TGA	[38]
SBA-15	PEI	0.04%/Ar	25	1.05	110	3/稳定	TGA	[39]

载体	胺种类	CO₂浓度/气氛	吸附温度/℃	CO₂吸附量/mmol·g^-1	再生温度/℃	循环次数/性能	测量方式	参考文献
EtSNTs	PEI	0.04%/N₂	30	1.05	100	8/N含量下降7%	PB	[25]
MCF	APS	0.04%/He	25	0.54	—	—	TGA	[26]
	MAPS	0.04%/He	25	0.17	—	—	TGA	[26]
MCF	PEI(800)	0.04%/Ar	25	1.74	110	—	TGA	[34]
	PEI(2500)	0.04%/Ar	25	1.05	110	3/稳定	TGA	[34]
	PAA	0.04%/Ar	25	0.86	110	—	TGA	[34]
纳米二氧化硅	PEI-LMW	空气	23	2.6	80	—	PB	[27]
	PEI-HMW	空气	23	2.0	80	—	PB	[27]
	PEI-Linear	空气	23	3.2	80	—	PB	[27]
白炭黑	PEI-ln	0.04%/N₂/O₂	25	2.34	140	—	IR	[28]
	PEI(800)	0.04%/N₂/O₂	25	2.44	140	—	IR	[28]
	PEI-M	0.04%/N₂/O₂	25	1.69	140	—	IR	[28]
	PEI-H	0.04%/N₂/O₂	25	1.67	140	—	IR	[28]
白炭黑	PEI(25000) 33%	0.042%	25	1.18 1.77（RH=67%）	85	—	IR	[40]
	PEI(25000) 50%	0.042%	25	1.70 1.41（RH=67%）	85	—	IR	[40]
硅胶	AEATPMS	0.04%～0.044%	25	0.4 0.44（RH=40%）	90	40/稳定	PB	[41]
HP2MG	TEPA	0.04%	35	2.50	80	—	TGA	[42]
CARiACT G10 HPV	PEI	0.04%/Ar	25	2.36	110	4/下降30%	TGA	[43]
	PEI+AP	0.04%/Ar	25	2.26	110	4/下降9%	TGA	[43]
	PEI+TP	0.04%/Ar	25	2.19	110	4/下降1%	TGA	[43]

Research progress of solid porous materials for direct CO₂ capture from air

直接空气捕碳固体多孔材料的研究进展

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载体/名称	胺种类	CO₂浓度/气氛	吸附温度/℃	CO₂吸附量/mmol·g^-1	再生温度/℃	循环次数/性能	测量方式	参考文献
PEI-syna50	PEI	0.04%/Ar	25	1.74	110	3/稳定	TGA	[39]
γ-Al₂O₃	PEI	0.04%/He	30	1.71（RH=50%）	—	—	IR	[45]
γ-Al₂O₃+5min steam	PEI	0.04%/He	30	1.96（RH=50%）	—	—	IR	[45]
γ-Al₂O₃ 40%	PEI	0.04%/He	30	1.23	—	—	TGA	[45]
Boehmite/alumina 40%	PEI	0.04%/He	30	1.12	—	—	TGA	[45]
K₂CO₃/Al₂O₃-750	—	0.04%～0.044%	25	0.93（RH=25%）	200	—	PB	[46]

载体/名称	胺种类	CO₂浓度/气氛	吸附温度/℃	CO₂吸附量/mmol·g^-1	再生温度/℃	循环次数/性能	测量方式	参考文献
Mg-MOF-74	—	0.04%	23.4	0.14（RH=49%）	—	—	TPD	[53]
Mg₂(dobpdc)	EN	0.039%	25	2.83	120	20/下降4%	vol.	[54]
Mg₂(dobdc)	EN	0.04%	22	1.51	110	4/稳定	TGA	[55]
Mg₂(dobpdc)	—	0.039%	25	0.13	—	—	vol.	[56]
Mg₂(dobpdc)	mmen	0.039%	25	1.05	150	6/稳定	TGA	[56]
Mg₂(dobdc)	N₂H₄	0.04%	25	3.89	130	—	TGA	[57]
Cr-MIL-101-SO₃H	TAEA	0.04%	20	1.72	80	15/稳定	vol.	[58]
HKUST-1	—	0.04%	23.4	0.05（RH=49%）	—	—	TPD	[59]
SIFSIX-3-Ni	—	0.04%	23.4	0.18（RH=49%）	—	—	TPD	[60]
SIFSIX-3-Cu	—	0.04%	25	1.24	—	—	vol.	[61]

载体/名称	胺种类	CO₂浓度/气氛	吸附温度/℃	CO₂吸附量/mmol·g^-1	再生温度/℃	循环次数/性能	测量方式	参考文献
HP20	PEI(600)	0.04%	25	2.26	100	5/稳定	PB	[64]
HP2MGL	PEI(600)	0.04%/N₂	25	1.96 3.16（RH=10%）	100	5/稳定	PB	[65]
HP2MGL	PEI(600)	0.04%/79.5%N₂/20.5%O₂	25	2.44（RH=10%）	—	—	PB	[65]
HP2MGL-CTAB	PEI(600)	0.04%/79.5%N₂/20.5%O₂	25	2.63（RH=10%）	—	—	PB	[65]
D201	季胺	0.04%	20	1.02（RH=21.2%）	变湿	—	TGA	[68]
D290	季胺	0.04%	20	1.03（RH=21.2%）	变湿	—	TGA	[68]

名称	载体	CO₂浓度/气氛	吸附温度 /℃	CO₂吸附量/mmol·g^-1	再生温度 /℃	循环次数/性能	测量方式	参考文献
RFAS4	甲醛、苯二酚APTES	0.04%/N₂	30	1.78（体积分数H₂O=0.15%）	80	10/略有下降	IR	[70]
CB-N-g-PCMS-OH^-	炭黑	压缩空气	15	0.36（RH=95%）	变湿	—	IR	[71]
Colloidal crystal	交联多孔聚合物	压缩空气	15	0.5（RH=95%）	变湿	—	IR	[72]
HIPE	高内相乳化体系	压缩空气	15	0.14（RH=95%）	变湿	—	IR	[72]
PPN-6-CH2DETA	PPN-6	0.04%/N₂/O₂	22	1.04	120	—	vol.	[73]
NPEI-SIPs	溶剂浸渍聚合物	0.04%/N₂	25	1.05 1.66（湿）	120	—	PB	[74]
AEAPDMS-NFC-FD	纳米纤维素	0.0506%	25	1.39（RH=40%）	80	20/稳定	IR	[75]
APDES-NFC	纳米纤维素	0.04%	23	1.11 2.13（RH=97%）	—	—	IR	[76]
PS-CC	聚苯乙烯	0.04%	20	0.57	变湿	—	IR	[77]
HIPES	交联多孔聚合物	压缩空气	15	0.72	变湿	15/稳定	IR	[78]
PEI snow	聚乙烯亚胺	空气	20±2	1.29	120	10/稳定	PB	[79]
PEI-CA-SiO₂	聚合物/二氧化硅整体纤维	0.0395%/He	35	0.59 1.6（RH=85%）	110	6/下降7%	TGA	[80]

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